CN101480606B - Adsorbing substance for absorbing heavy metal ion and preparation method thereof - Google Patents
Adsorbing substance for absorbing heavy metal ion and preparation method thereof Download PDFInfo
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- CN101480606B CN101480606B CN 200810246170 CN200810246170A CN101480606B CN 101480606 B CN101480606 B CN 101480606B CN 200810246170 CN200810246170 CN 200810246170 CN 200810246170 A CN200810246170 A CN 200810246170A CN 101480606 B CN101480606 B CN 101480606B
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Abstract
The invention discloses an adsorbent for adsorbing heavy metal ions, and the preparation method of the adsorbent. The invention is characterized in that a silane coupling agent and acid anhydride are in epoxy ring cleavage reaction in inert atmosphere or air at the temperature of minus 78 to 200 DEG C, wherein the mol ratio of the silane coupling agent to the acid anhydride is 1 : 2 to 20; after the reaction product is dissolved by a solvent, halogenated alkane is added to the solution according to the mol ratio of two to ten times of the silane coupling agent, the quaternization reaction is carried out at the temperature of 0 to 200 DEG C, and then, the product generated by the quaternization reaction is cleaned with water or ethanol and is dried to obtain the adsorbent for adsorbing the heavy metal ions. In the adsorbent, acidic groups are arranged on both sides of a molecular backbone, and basic groups are positioned on the molecular backbone. The adsorbent has stronger capability for adsorbing heavy metal ions, such as Pb2+, Cu2+ and the like in the solution, and can be used for adsorption separation and purification treatment of waste water containing heavy metal ions.
Description
Technical field
The invention belongs to technical field of waste water processing, particularly be used for the adsorbent of Adsorption of Heavy Metal Ions and utilize epoxy addition reaction and the preparation method of quaterisation.
Background technology
The preparation method of a kind of adsorbent for heavy metal that Chinese patent 200410070107.X proposes is the template agent with the non-ionic polyalcohol, with (MeO)
3SiCH
2CH
2Si (OMe)
3(MeO)
3SiCH
2CH
2CH
2To be that the copolymerization of silicon source is synthetic contain the SH mixture-and the organic/inorganic hybridization material of SH adsorption site comes Adsorption of Heavy Metal Ions; But the employed raw material of this method (MeO)
3SiCH
2CH
2CH
2SH has stronger smell, to environment and human body harmful; And the easy oxidation in air of-SH group becomes the semi-annular jade pendant acidic group, and its using value is limited.
A kind of novel silica gel loaded cross-linked chitosan adsorbent for heavy metal that Chinese patent 200510045500.8 proposes is to contain epoxide group and water miscible inorganic silane reagent γ-Huan Yangbingyangbingjisanjiayangjiguiwan is that raw material comes cross-linked chitosan; The adsorbent of this method preparation only contains a kind of functional group, has the shortcoming that radical species is unadjustable, adsorption capacity weak, desorb is difficult, and raw material variety is single, the source is limited, is difficult to large-scale industrial and uses.
So far do not see report about the adsorbent that is used for Adsorption of Heavy Metal Ions that contains acid and basic group.
Summary of the invention
The present invention proposes a kind of adsorbent that is used for Adsorption of Heavy Metal Ions and preparation method thereof, overcoming the above-mentioned defective of prior art, for the adsorbing separation of heavy metal ions in wastewater provides a new approach.
The preparation of adsorbent method that is used for Adsorption of Heavy Metal Ions of the present invention, it is characterized in that: in inert atmosphere or air, under-78～200 ℃ of temperature conditions, silane coupler and acid anhydrides 1: 2 in molar ratio～20 are carried out the epoxy addition reaction, with products therefrom with dissolution with solvents after, in above-mentioned solution, add halogenated alkane, its addition in mole be silane coupler 2-10 doubly, under 0-200 ℃ of temperature conditions, carry out quaterisation, product water behind the quaterisation or ethanol are cleaned, drying promptly obtains can be used for the adsorbent of Adsorption of Heavy Metal Ions.
Described epoxy addition reaction is meant in inert atmosphere or air, and under-78～200 ℃ of temperature conditions, under the effect of water or diluted acid, epoxy side group that contains on silane coupler and the acid anhydrides or end group open loop generate respective substance; It is watery hydrochloric acid, dilute sulfuric acid, phosphoric acid,diluted or the spirit of vinegar of 0.0001-0.1 that used diluted acid can be selected molar concentration for use.
Described quaterisation, be meant in inert atmosphere or air, under 0-200 ℃ temperature conditions, silane coupler and anhydride reaction products therefrom are dissolved in the solvent, according to the mol ratio silane coupler: the ratio of halogenated alkane=1: 2-10 adds halogenated alkane, back flow reaction 1-48 hour again, on strand, obtain alkyl.
Described silane coupler is siloxanes or the halosilanes that contains the ammonia alkyl.
Described acid anhydrides is selected from phthalic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride or the pyrovinic acid acid anhydride that contains epoxy-terminated or side group.
Described solvent is selected from N, dinethylformamide, N, N-dimethylacetylamide, oxolane, acetone or ethyl acetate.
Described halogenated alkane is selected from iodomethane, bromoethane, chloroethanes, 1,2-Bromofume or 1,2-dichloroethanes.
Described drying can be selected convective drying, conductive drying, infrared drying, microwave drying, freeze drying for use, chemical hygroscopic drying or mechanical dehydration drying.
Also can react in the resulting product at epoxy addition, by silane coupler: solvent: water: the mol ratio of catalyst=1: 2-20: 0.01-8: 0.001-0.01 adds entry and catalyst, carry out quaterisation with adding halogenated alkane after the dissolution with solvents, with quaterisation products therefrom water or ethanol clean, drying, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions; Catalyst system therefor is selected from hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, trimethylamine, triethylamine or stannous octoate.
Also can react in the resulting product at epoxy addition, be silane coupler in molar ratio: solvent: alkoxide=1: 2-20: 0.01-10 adds the alkoxide of Si, Ti or Zr, carry out quaterisation with adding halogenated alkane after the dissolution with solvents, products therefrom water or ethanol clean, drying, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions.
Also epoxy addition can be reacted resulting product and film on matrix after with dissolution with solvents and obtain diaphragm, be with the dry xerogel layer that forms of diaphragm in the environment of 50-90% at 0-90 ℃, relative humidity then; Again xerogel layer is carried out quaterisation after the cooling, with reacted diaphragm water or ethanol clean, drying, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions.
Also the product of quaterisation can be filmed on matrix after with dissolution with solvents and obtain diaphragm, then 0-90 ℃, relative humidity be in the environment of 50-90% with the diaphragm drying, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions.
Described matrix can be selected Al for use
2O
3Pottery, SiO 2-ceramic, titanium dioxide ceramic, zirconia ceramic, polyethylene film, polyfluortetraethylene plate, glass plate, woven dacron, polyamide fabric, glass fabric, nylon cloth or nonwoven.
Described filming can select for use knifing, sprinkling to film, flood and film, flow and film or spin-coating.
The adsorbent that is used for Adsorption of Heavy Metal Ions of employing method for preparing of the present invention is characterised in that its structural formula can be expressed as follows:
Adopt the preparation-obtained adsorbent of the inventive method to Pb in the aqueous solution
2+, Cu
2+Have stronger adsorption capacity etc. heavy metal ion, can be used for containing the adsorbing separation and the purified treatment of effluent containing heavy metal ions.
Compared with prior art, the present invention has adopted epoxy addition and quaterisation preparation to be used for the adsorbent of Adsorption of Heavy Metal Ions, and grafting has acid and two kinds of groups of alkalescence on its strand, and its outstanding feature is:
(1) can increase adsorption capacity by the electrostatic attraction effect Adsorption of Heavy Metal Ions of acidic-group; Repulsive interaction by basic group makes heavy metal ion be easy to desorb from the adsorbent, improves its power of regeneration; The adsorbent that has overcome prior art for preparing only contains the simple function group, the shortcoming that adsorption capacity is weak, desorption is difficult;
(2) can regulate the adsorptive selectivity of ABSORBENTS ABSORPTION metal ion by regulating content acid and basic group in the adsorbent, overcome the shortcoming that adsorbent group kind is unadjustable, applicability is relatively poor of prior art for preparing, thereby the adsorbent that makes the present invention be used for Adsorption of Heavy Metal Ions can satisfy the requirement of various wastewater system to the adsorbing separation and the purified treatment of heavy metal ion.
With Chinese patent ZL 200410070107.X report be the template agent with the non-ionic polyalcohol, with (MeO)
3SiCH
2CH
2Si (OMe)
3(MeO)
3SiCH
2CH
2CH
2To be that the copolymerization of silicon source is synthetic contain the SH mixture-and the organic/inorganic hybridization material of SH adsorption site comes the method for Adsorption of Heavy Metal Ions to compare, preparation method of the present invention is simple, safe operation process, cleaning, strong to heavy metal ion adsorbed ability, and adsorptive selectivity is good.
With Chinese patent ZL 200510045500.8 report be that the method that raw material comes cross-linked chitosan to prepare adsorbent for heavy metal is compared to contain epoxide group with water miscible inorganic silane reagent γ-Huan Yangbingyangbingjisanjiayangjiguiwan; preparation technology of the present invention is simple; raw material sources are wide; the heat resistance height can large-scale production.
Description of drawings
Fig. 1 is the examination of infrared spectrum figure of the adsorbent for preparing among the embodiment 1.
The specific embodiment
Below further describe a kind of adsorbent that is used for Adsorption of Heavy Metal Ions of the present invention and preparation method thereof by specific embodiment.
Embodiment 1. is with reactant ratio pyromellitic dianhydride (PMDA): anilinomethyl triethoxysilane (ND-42): bromoethane=preparations in 4: 1: 6 are used for the adsorbent of Adsorption of Heavy Metal Ions
First bubbling air or nitrogen in the 250ml there-necked flask of agitator is housed add 15mlN then, and dinethylformamide (DMF) adds 10.12g pyromellitic dianhydride (PMDA) under bubbling air or condition of nitrogen gas; Under constantly stirring, make its dissolving, drip 2.5ml quality percentage composition again and be 95% anilinomethyl triethoxysilane (ND-42) solution and carry out the epoxy addition reaction, the mol ratio of control reactant is pyromellitic dianhydride (PMDA): anilinomethyl triethoxysilane (ND-42)=4: 1 (promptly keep PMDA excessive).In adding the process of silane coupler, can find the two vigorous reaction and emit a large amount of heat, show that reaction carries out, and the very fast dissolving of pyromellitic dianhydride.When the large percentage of pyromellitic dianhydride (PMDA) and anilinomethyl triethoxysilane (ND-42), pyromellitic dianhydride dissolves slower in DMF solution, at this moment can suitably heat with fast reaction speed.Take in the present embodiment under 50 ℃ of temperature conditions, to continue to stir to guarantee the complete of epoxy addition reaction; The watery hydrochloric acid that also can add 0.1M is accelerated the speed of epoxy addition reaction.After 12h is carried out in reaction, can obtain the hydridization precursor solution.Because the sterically hindered effect of phenyl ring makes polymer can not form polyimide structures in heating process, can only form polyurea copolymers, thus on resulting polymer molecule side chain a kind of acid carboxyl of grafting.
The above-mentioned about 17.5ml hydridization precursor solution for preparing is dissolved in the 10mlDMF solution again, under 180 ℃ of temperature conditions, add the 15ml bromoethane and carry out quaterisation 24h, make grafting alkyl on the strand, obtain a kind of basic group, to react back gained material spend ionized water or ethanol clean 3 times, behind 200 ℃ of convective drying 24h, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions, it contains carboxyl (acidic-group) and amino (basic group) two kinds of ion-exchange groups simultaneously.For guaranteeing the ability that reaches raising adsorbents adsorb heavy metal ion fully of ring-opening reaction, in present embodiment preparation of adsorbent process, make pyromellitic dianhydride keep excessive.
Fig. 1 has provided the examination of infrared spectrum collection of illustrative plates of the resulting adsorbent of preparation in the present embodiment, and wherein dotted line A is the examination of infrared spectrum collection of illustrative plates of epoxy addition reaction products therefrom; Solid line B is the examination of infrared spectrum collection of illustrative plates of the product behind the quaterisation.As can be seen from Fig. 1 :～1712cm
-1The place is on the carboxyl-absworption peak of CO, and 3400cm
-1The place is-absworption peak of OH, and illustrate the epoxy addition reaction has taken place really.After the quaterisation, at 1500cm
-1The absworption peak at place disappears, at 3433cm
-1The absworption peak of the appearance-NH of place shows that quaterisation takes place really.～1108cm
-1The place is the characteristic peak of Si-O-Si and Si-O-C, illustrate and have inorganic component Si in this material, and contain carboxyl (acidic-group) and amino (basic group) two kinds of charged groups, so the resulting adsorbent of preparation is the inorganic-organic hybridization material in the present embodiment.
The adsorbent for preparing in the present embodiment is carried out Adsorption of Heavy Metal Ions test, and experimentation is as follows: take by weighing the 1g sample, clean 3 times with deionized water, cooling off behind the dry 4h down at 120 ℃, grind broken again and claim its weight, add the Pb (NO of 0.01mol/L
3)
2Solution 40ml adsorbs 24h under 45 ℃ of temperature conditions, and then adsorbs the concentration of lead ion in the residual solution of back with the 0.01mol/LEDTA standard solution titration.Adopt same experimental procedure, take by weighing the 1g sample, clean 3 times, cooling off behind the dry 4h down, grind broken again and claim its weight, add the Cu (NO of 0.01mol/L at 120 ℃ with deionized water
3)
240ml adsorbs 24h, and then uses 0.01mol/LNa under 45 ℃ of temperature conditions
2S
2O
3The concentration of copper ion in the residual solution of standard solution titration absorption back.Experimental result shows: under 45 ℃ of temperature conditions to Cu
2+Adsorbance is 0.045-0.12mmol/g, to Pb
2+Adsorbance is 0.17-0.51mmol/g; As seen the heavy metal ion of the hybrid material for preparing in the present embodiment in can adsorption aqueous solution; And because this charged hybrid material is to Pb
2+Adsorb comparatively obvious, so it can optionally adsorb the heavy metal Pb in the waste water
2+Ion.
The above-mentioned product that has adsorbed heavy metal ion is carried out the desorption experiment, process is as follows: under 25 ℃ of temperature conditions, take by weighing 1g and adsorbed the adsorbent of heavy metal copper ion, it is joined the nitric acid that the 25ml molar concentration is 1mol/L respectively, in sulfuric acid or the hydrochloric acid solution, after placing 1h, adopt the method for the used solution titration of above-mentioned adsorption test to measure the concentration of the heavy metal copper ion that desorb is got off in the solution, calculate the desorption rate by following formula then: the percentage of (weight of the heavy metal ion that desorption is got off)/(gross weight of sample before the desorption) x100%=desorption rate.Equally, under 25 ℃ of temperature conditions, take by weighing 1g and adsorbed the adsorbent of heavy metal lead ion, it is joined in the EDTA solution that the 25ml molar concentration is 1mol/L, the method of the used solution titration of the above-mentioned adsorption test of employing is measured the concentration of the heavy metal lead ion that desorb is got off in the solution behind the placement 1h, calculates the desorption rate again.Experimental result shows: the desorption rate of copper ion is 96.4% when carrying out the desorption test in salpeter solution, the desorption rate of copper ion is 89.1% when carrying out the desorption test in sulfuric acid solution, and the desorption rate of copper ion is 84.9% when carrying out the desorption test in hydrochloric acid solution; This explanation uses conventional acid reagent that the copper ion desorption is come out.The desorption rate of lead ion is 87.6% when carrying out the desorption test in EDTA solution, and this explanation general reagent just can make the lead ion desorption come out.
In sum: having prepared a kind of adsorbent that can be used for Adsorption of Heavy Metal Ions in the present embodiment, is the inorganic-organic hybridization material, contains acid and two kinds of ionic groups of alkalescence.Owing in the quaterisation process, used nontoxic DMF solvent, overcome prior art and used poisonous chloromethyl ether to carry out the shortcoming of quaterisation, meet cleaner production, requirements of green environmental protection.
Embodiment 2. is with reactant ratio pyromellitic dianhydride (PMDA): anilinomethyl triethoxysilane (ND-42): bromoethane=preparations in 4: 1: 6 are used for the adsorbent diaphragm of Adsorption of Heavy Metal Ions
Adopt similarly to Example 1 device and operating procedure, under-78 ℃ of temperature conditions, with 20ml solvent N, dinethylformamide (DMF) dissolving 10g raw material, under 30 ℃ of temperature, carry out quaterisation again,, use this solution then at Al with the product of quaterisation DMF dissolution with solvents
2O
3Dipping is filmed to obtaining diaphragm on the ceramic matrix, is dry 12 hours of 70% environment middle infrared (Mid-IR) with diaphragm being placed on 200 ℃, relative humidity, obtains hybridized film, and the diaphragm of this hybridized film is the adsorbent that can be used for Adsorption of Heavy Metal Ions.For guaranteeing the ability that reaches raising adsorbents adsorb heavy metal ion fully of ring-opening reaction, in the preparation of adsorbent process, make pyromellitic dianhydride keep excessive.
The experimentation that the adsorbent for preparing in the present embodiment is carried out Adsorption of Heavy Metal Ions is as follows: take by weighing the 1g sample, clean 3 times with deionized water, cooling off behind the dry 4h down at 120 ℃, grind broken again and take by weighing its weight, add the Pb (NO of 0.01mol/L
3)
2Solution 40ml adsorbs 24h under 35 ℃ of temperature conditions, and then adsorbs the concentration of lead ion in the residual solution of back with the 0.01mol/LEDTA standard solution titration.Equally, take by weighing the 1g sample, clean 3 times,, grind broken again and take by weighing its weight, add the Cu (NO of 0.01mol/L at 120 ℃ of dry 4h down with deionized water
3)
240ml adsorbs 24h, and then uses 0.01mol/LNa under 45 ℃ of temperature conditions
2S
2O
3The concentration of copper ion in the residual solution of standard solution titration absorption back.The experiment of Adsorption of Heavy Metal Ions shows: under 35 ℃ of temperature conditions, this hybridized film is to Cu
2+Adsorbance is 0.066-0.11mmol/g, to Pb
2+Adsorbance is 0.13-0.48mmol/g; As seen this hybridized film can Adsorption of Heavy Metal Ions; Because it is to Pb
2+Adsorb comparatively obvious, so it can optionally adsorb the Pb in the waste water
2+Ion.
The above-mentioned adsorbent that has adsorbed heavy metal ion is carried out the desorption experiment, process is as follows: take by weighing the made adsorbent that 1g has adsorbed the heavy metal copper ion under 25 ℃ of temperature conditions, it is joined respectively in nitric acid, hydrochloric acid or the sulfuric acid solution that the 25ml molar concentration is 1mol/L, the concentration of the heavy metal copper ion that gets off with desorb in the 0.01mol/LEDTA standard solution titration solution behind the placement 1h is calculated the desorption rate by following formula: the percentage of (weight of the heavy metal ion that desorption is got off)/(gross weight of sample before the desorption) x100%=desorption rate then.Equally, under 25 ℃ of temperature conditions, take by weighing 1g and adsorbed the adsorbent of heavy metal lead ion, it is joined in the EDTA solution that the 25ml molar concentration is 1mol/L, the concentration of the heavy metal lead ion that gets off with desorb in the 0.01mol/LEDTA standard solution titration solution behind the placement 1h is calculated the desorption rate again.Above-mentioned desorption experiment shows: the desorption rate of copper ion is 97.6% when carrying out the desorption test in salpeter solution, the desorption rate of copper ion is 87.8% when carrying out the desorption test in hydrochloric acid solution, and the desorption rate of copper ion is 85.7% when carrying out the desorption test in sulfuric acid solution; This explanation uses conventional acid reagent just can make the copper ion desorption.The desorption rate of lead ion is 84.6% when carrying out the desorption test in EDTA solution, and this explanation general reagent just can make the lead ion desorption come out.
In sum: the hybridized film for preparing in the present embodiment can be used for the heavy metal ion in the adsorption aqueous solution.Because what use in the quaterisation process is nontoxic DMF solvent, overcome prior art and used poisonous chloromethyl ether to carry out the shortcoming of quaterisation, meet cleaner production, requirements of green environmental protection.
Embodiment 3. is with reactant ratio pyromellitic dianhydride (PMDA): anilinomethyl triethoxysilane (ND-42): catalyst: bromoethane=4: 1: 0.001: 6 preparations are used for the adsorbent of Adsorption of Heavy Metal Ions
Adopt similarly to Example 1 device and operating procedure, under 60 ℃ of temperature conditions, be silane coupler in molar ratio in the prepared hydridization precursor solution in embodiment 1: water: catalyst=1: 0.01: 0.001 adds deionized water and catalyst of triethylamine, be stirred to and obtain uniform solution, then this solution is carried out quaterisation, the mol ratio of pressing 6 times of silane couplers during quaterisation adds the halogenated alkane bromoethane in above-mentioned solution, thereby make it contain alkalescence and acidic-group, back gained material be will react and ionized water or ethanol cleaning spent, dry 12h under 150 ℃ of temperature conditions, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions, it contains carboxyl (acidic-group) and amino (basic group).For guaranteeing the ability that reaches raising adsorbents adsorb heavy metal ion fully of ring-opening reaction, in the preparation of adsorbent process, make pyromellitic dianhydride keep excessive.
The adsorbent for preparing in the present embodiment is carried out the Adsorption of Heavy Metal Ions test, and experimental result shows: to Cu
2+Adsorbance is 0.038-0.12mmol/g, to Pb
2+Adsorbance is 0.15-0.47mmol/g; As seen this charged hybrid material can Adsorption of Heavy Metal Ions; Because this charged hybrid material is to Pb
2+Adsorb comparatively obvious, so it can optionally adsorb the Pb in the waste water
2+Ion.
The above-mentioned product that has adsorbed heavy metal ion is carried out the desorption experiment, experimental result shows: the desorption rate of copper ion is 96.4% when carrying out the desorption test in salpeter solution, the desorption rate of copper ion is 84.9% when carrying out the desorption test in hydrochloric acid solution, and the desorption rate of copper ion is 89.1% when carrying out the desorption test in sulfuric acid solution; This explanation uses conventional acid reagent just can make the copper ion desorption.The desorption rate of lead ion is 85.8% when carrying out the desorption test in EDTA solution, and this explanation general reagent just can make the lead ion desorption come out.
In sum: present embodiment has prepared the adsorbent that can be used for Adsorption of Heavy Metal Ions, and it contains acid and two kinds of ionic groups of alkalescence.
Embodiment 4. is with reactant ratio pyromellitic dianhydride (PMDA): anilinomethyl triethoxysilane (ND-42): butyl titanate: bromoethane=4: 1: 2: 6 preparations are used for the adsorbent of Adsorption of Heavy Metal Ions
Adopt similarly to Example 1 device and operating procedure, stirring reaction under-78 ℃ of temperature conditions, preparation hydridization precursor solution; Then it is dissolved in N, dinethylformamide (DMF), add butyl titanate, stir, the mol ratio of regulating them is 4: 1: 2: 6, under 25 ℃ of conditions, continue to stir 12h, to obtaining sol-gel, on matrix, film to obtaining being coated with rete with this sol-gel, add bromoethane again and carry out quaterisation being coated with rete.For guaranteeing the ability that reaches raising adsorbents adsorb heavy metal ion fully of ring-opening reaction, in the preparation of adsorbent process, make pyromellitic dianhydride keep excessive.
The above-mentioned reacted rete that is coated with is cleaned, behind 200 ℃ of dry 12h, can obtain containing the charged hybridized film of acid and basic group; Promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions;
Examination of infrared spectrum the analysis showed that: 900-1150cm
-1The place is the strong absworption peak of Si-O-Ti, illustrate titanium by grafting successfully to strand.1100cm
-1The place is the strong absworption peak of Si-O-C and Si-O-Si, 1730cm
-1The place is the absworption peak of carboxyl.This explanation products therefrom is a hybrid material.
The adsorbent for preparing in the present embodiment is carried out the Adsorption of Heavy Metal Ions test, and experiment shows: to Cu
2+Adsorbance is 0.044-0.12mmol/g, to Pb
2+Adsorbance is 0.23-0.46mmol/g; As seen this hybrid material can Adsorption of Heavy Metal Ions.
The above-mentioned product that has adsorbed heavy metal ion is carried out the desorption experiment, the result shows: the desorption rate of copper ion is 97.2% when carrying out the desorption test in salpeter solution, the desorption rate of copper ion is 82.8% when carrying out the desorption test in hydrochloric acid solution, and the desorption rate of copper ion is 91.4% when carrying out the desorption test in sulfuric acid solution; This explanation uses conventional acid reagent just can make the copper ion desorption.The desorption rate of lead ion is 82.7% when carrying out the desorption test in EDTA solution, and this explanation general reagent just can make the lead ion desorption come out.
Comprehensively above-mentioned, present embodiment has prepared the adsorbent that can be used for Adsorption of Heavy Metal Ions, and it contains acid and alkaline two kinds of different ionic groups.
Embodiment 5. is with reactant ratio pyromellitic dianhydride (PMDA): anilinomethyl triethoxysilane (ND-42): butyl titanate: bromoethane=4: 1: 2: 6 preparations are used for the adsorbent of Adsorption of Heavy Metal Ions
Adopt similarly to Example 4 device, operating procedure and proportion scale, stirring reaction under 40 ℃ of temperature conditions, preparation hydridization precursor solution; Then it is dissolved in N, dinethylformamide (DMF) adds butyl titanate, stirs, and adds bromoethane then and carries out quaterisation; The mol ratio of regulating them is 4: 1: 2: 6, under 25 ℃ of conditions, continue to stir 12h, and to obtaining sol-gel, this sol-gel directly can be obtained being used for the adsorbent of Adsorption of Heavy Metal Ions behind 200 ℃ of convective drying 12h.
Examination of infrared spectrum the analysis showed that: 900-1150cm
-1The place is the strong absworption peak of Si-O-Ti, illustrate titanium by grafting successfully to strand.1100cm
-1The place is the strong absworption peak of Si-O-C and Si-O-Si, 1730cm
-1The place is the absworption peak of carboxyl.This explanation products therefrom is a hybrid material.
The adsorbent for preparing in the present embodiment is carried out the Adsorption of Heavy Metal Ions test, and experiment shows: to Cu
2+Adsorbance is 0.041-0.15mmol/g, to Pb
2+Adsorbance is 0.26-0.51mmol/g; As seen this hybrid material can Adsorption of Heavy Metal Ions.
Comprehensively above-mentioned: present embodiment has prepared the adsorbent that can be used for Adsorption of Heavy Metal Ions, and it contains acid and two kinds of groups of alkalescence.
Embodiment 6. is with reactant ratio pyromellitic dianhydride (PMDA): anilinomethyl triethoxysilane (ND-42): bromoethane=preparations in 4: 1: 6 are used for the adsorbent of Adsorption of Heavy Metal Ions
In the 250ml there-necked flask, load onto agitator, bubbling air or nitrogen, add 15mlN earlier, dinethylformamide (DMF), the pyromellitic dianhydride (PMDA) of adding 20g under bubbling air or condition of nitrogen gas; Under agitation drip anilinomethyl triethoxysilane (ND-42) solution 5ml then, under 50 ℃ of temperature conditions, continue to stir.Reaction is carried out obtaining the hydridization precursor solution behind the 12h; Because sterically hindered acting on the strand can not form polyimide structures, thereby makes its carboxyl that contains a kind of acidity, this acidic-group is positioned on the side chain of strand; So just obtain a kind of hydridization presoma that contains acidic-group;
The hydridization presoma of above-mentioned preparation is dissolved in the DMF solution of 20ml, floods on matrix with this solution and film to obtaining being coated with rete; To be coated with in the rete immersion 30ml bromoethane solution and carry out quaterisation 24h, make grafting alkyl on the strand, obtain a kind of basic group, reaction back gained diaphragm cleaning 3 times, 200 ℃ of following convective drying 12h are promptly obtained can be used for the adsorbent of Adsorption of Heavy Metal Ions; It contains carboxyl and amino two kinds of different acidity and basic group, and it is to Pb in the solution
2+, Cu
2+Also have stronger adsorption capacity etc. heavy metal ion, can be used for containing the adsorbing separation of effluent containing heavy metal ions.For guaranteeing the ability that reaches raising adsorbents adsorb heavy metal ion fully of ring-opening reaction, in the preparation of adsorbent process, make pyromellitic dianhydride keep excessive.
Infrared test shows :～1730cm
-1The place is on the carboxyl-absworption peak of CO, and 3400cm
-1The place is-absworption peak of OH, and illustrate the epoxy addition reaction has taken place really.After the quaterisation, at 1500cm
-1The absworption peak at place disappears, at 3433cm
-1The place occurred-absworption peak of NH, show that quaterisation takes place really.～1100cm
-1The place is the characteristic absorption peak of Si-O-Si and Si-O-C, illustrates to contain inorganic component Si in this material.Because in this hybrid material, so it is the inorganic-organic hybridization material.
The adsorbent for preparing in the present embodiment is carried out the Adsorption of Heavy Metal Ions test, and experiment shows: to Cu
2+Adsorbance is 0.035-0.11mmol/g, to Pb
2+Adsorbance is 0.15-0.47mmol/g; As seen this hybrid material can Adsorption of Heavy Metal Ions; And because this charged hybrid material is to Pb
2+Adsorb comparatively obvious, so can optionally adsorb Pb in the waste water
2+Ion.
The above-mentioned product that has adsorbed heavy metal ion is carried out the desorption experiment, the result shows: the desorption rate of copper ion is 97.2% when carrying out the desorption test in salpeter solution, the desorption rate of copper ion is 86.3% when carrying out the desorption test in hydrochloric acid solution, and the desorption rate of copper ion is 91.4% when carrying out the desorption test in sulfuric acid solution; This explanation uses conventional acid reagent just can make the copper ion desorption.The desorption rate of lead ion is 89.5% when carrying out the desorption test in EDTA solution, and this explanation general reagent just can make the lead ion desorption come out.
In sum: present embodiment has prepared the adsorbent that can be used for Adsorption of Heavy Metal Ions.
Embodiment 7. is with reactant ratio pyromellitic dianhydride (PMDA): anilinomethyl triethoxysilane (ND-42): bromoethane=preparations in 4: 1: 5 are used for the adsorbent of Adsorption of Heavy Metal Ions
Adopt similarly to Example 1 device and operating procedure, carry out the epoxy addition reaction under 70 ℃ of temperature conditions, reaction is carried out quaterisation after finishing again; In the quaterisation process, suitably control the rate of addition and the addition of bromoethane, thereby regulate bromination degree percentage＜50%; The percentage of bromination degree can be calculated by following formula: the percentage of (example weight after the bromination)/(example weight before the bromination) x100%=bromination degree.To react back gained material spend ionized water or ethanol clean 3 times, under 150 ℃ of temperature convective drying 12h, can obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions.Owing in course of reaction, controlled the weight percentage of basic group, so the absorption property of adsorbent can effectively be regulated.
The adsorbent for preparing in the present embodiment is carried out Adsorption of Heavy Metal Ions test, and experiment shows: under 25 ℃ of temperature conditions to Cu
2+Adsorbance is 0.032-0.08mmol/g, to Pb
2+Adsorbance is 0.11-0.36mmol/g; As seen this hybrid material can Adsorption of Heavy Metal Ions; Because it is to Pb
2+Adsorb comparatively obvious, so can optionally adsorb Pb in the waste water
2+Ion.
The above-mentioned product that has adsorbed heavy metal ion is carried out the desorption experiment, the result shows: the desorption rate of copper ion is 98.3% when carrying out the desorption test in salpeter solution, the desorption rate of copper ion is 89.6% when carrying out the desorption test in hydrochloric acid solution, and the desorption rate of copper ion is 87.4% when carrying out the desorption test in sulfuric acid solution; This explanation uses conventional acid reagent just can make the copper ion desorption.The desorption rate of lead ion is 89.3% when carrying out the desorption test in EDTA solution, and this explanation general reagent just can make the lead ion desorption come out.
In sum: present embodiment has prepared the adsorbent that can be used for Adsorption of Heavy Metal Ions.Owing in the quaterisation process, can artificially regulate the weight percentage of group, overcome the shortcoming that adsorbent group kind is unadjustable, applicability is relatively poor of prior art for preparing, thereby the adsorbent that makes the present invention be used for Adsorption of Heavy Metal Ions can satisfy the requirement of various wastewater system to the adsorbing separation and the purified treatment of heavy metal ion.
The amount of the material that relates in the above-mentioned embodiment of the present invention, temperature, the time, parameters such as concentration all can fluctuate in ± 15% scope.
Claims (7)
1. preparation of adsorbent method that is used for Adsorption of Heavy Metal Ions, it is characterized in that: in inert atmosphere or air, under-78～200 ℃ of temperature conditions, with silane coupler and acid anhydrides 1: 2 in molar ratio～20, carry out the epoxy addition reaction under the effect of water or diluted acid, used diluted acid is watery hydrochloric acid, dilute sulfuric acid, phosphoric acid,diluted or the spirit of vinegar of molar concentration 0.0001-0.1; With products therefrom with dissolution with solvents after, in above-mentioned solution, add halogenated alkane, its addition in mole be silane coupler 2-10 doubly, under 0-200 ℃ of temperature conditions, carried out quaterisation in back flow reaction 1-48 hour; With the product water of quaterisation or ethanol clean, drying, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions; Described silane coupler is siloxanes or the halosilanes that contains the ammonia alkyl; Described acid anhydrides is phthalic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride or the pyrovinic acid acid anhydride that contains epoxy-terminated or side group.
2. the preparation of adsorbent method that is used for Adsorption of Heavy Metal Ions according to claim 1 is characterised in that described solvent is selected from N, dinethylformamide, N, N-dimethylacetylamide, oxolane, acetone or ethyl acetate.
3. the preparation of adsorbent method that is used for Adsorption of Heavy Metal Ions according to claim 1 is characterised in that described halogenated alkane is selected from iodomethane, bromoethane, chloroethanes, 1,2-Bromofume or 1,2-dichloroethanes.
4. preparation of adsorbent method that is used for Adsorption of Heavy Metal Ions, it is characterized in that: in inert atmosphere or air, under-78～200 ℃ of temperature conditions, with silane coupler and acid anhydrides 1: 2 in molar ratio～20, carry out the epoxy addition reaction under the effect of water or diluted acid, used diluted acid is watery hydrochloric acid, dilute sulfuric acid, phosphoric acid,diluted or the spirit of vinegar of molar concentration 0.0001-0.1; In the product that described epoxy addition reaction obtains, by silane coupler: solvent: water: the mol ratio of catalyst=1: 2-20: 0.01-8: 0.001-0.01 adds entry and catalyst, with adding halogenated alkane after the dissolution with solvents, its addition in mole be silane coupler 2-10 doubly, under 0-200 ℃ of temperature conditions, carried out quaterisation in back flow reaction 1-48 hour, with the product water of gained behind the quaterisation or ethanol clean, drying, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions; Described silane coupler is siloxanes or the halosilanes that contains the ammonia alkyl; Described acid anhydrides is phthalic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride or the pyrovinic acid acid anhydride that contains epoxy-terminated or side group; Catalyst system therefor is selected from hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, trimethylamine, triethylamine or stannous octoate.
5. preparation of adsorbent method that is used for Adsorption of Heavy Metal Ions, it is characterized in that: in inert atmosphere or air, under-78～200 ℃ of temperature conditions, with silane coupler and acid anhydrides 1: 2 in molar ratio～20, carry out the epoxy addition reaction under the effect of water or diluted acid, used diluted acid is watery hydrochloric acid, dilute sulfuric acid, phosphoric acid,diluted or the spirit of vinegar of molar concentration 0.0001-0.1; In the product that described epoxy addition reaction obtains, be silane coupler in molar ratio: solvent: alkoxide=1: 2-20: 0.01-10 adds the alkoxide of Si, Ti or Zr, with in gained solution, adding halogenated alkane after the dissolution with solvents, its addition in mole be silane coupler 2-10 doubly, under 0-200 ℃ of temperature conditions, carried out quaterisation in back flow reaction 1-48 hour, with the product water of gained behind the quaterisation or ethanol clean, drying, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions; Described silane coupler is siloxanes or the halosilanes that contains the ammonia alkyl; Described acid anhydrides is phthalic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride or the pyrovinic acid acid anhydride that contains epoxy-terminated or side group.
6. preparation of adsorbent method that is used for Adsorption of Heavy Metal Ions, it is characterized in that: in inert atmosphere or air, under-78～200 ℃ of temperature conditions, with silane coupler and acid anhydrides 1: 2 in molar ratio～20, carry out the epoxy addition reaction under the effect of water or diluted acid, used diluted acid is watery hydrochloric acid, dilute sulfuric acid, phosphoric acid,diluted or the spirit of vinegar of molar concentration 0.0001-0.1; The product that the reaction of described epoxy addition is obtained is filmed on matrix after with dissolution with solvents and is obtained diaphragm, is with the dry xerogel layer that forms of diaphragm in the environment of 50-90% at 0-90 ℃, relative humidity then; Again xerogel layer and halogenated alkane are carried out quaterisation after the cooling, the halogenated alkane addition in mole be silane coupler 2-10 doubly, under 0-200 ℃ of temperature conditions back flow reaction 1-48 hour, with reacted diaphragm water or ethanol clean, drying, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions; Described silane coupler is siloxanes or the halosilanes that contains the ammonia alkyl; Described acid anhydrides is phthalic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride or the pyrovinic acid acid anhydride that contains epoxy-terminated or side group.
7. preparation of adsorbent method that is used for Adsorption of Heavy Metal Ions, it is characterized in that: in inert atmosphere or air, under-78～200 ℃ of temperature conditions, with silane coupler and acid anhydrides 1: 2 in molar ratio～20, carry out the epoxy addition reaction under the effect of water or diluted acid, used diluted acid is watery hydrochloric acid, dilute sulfuric acid, phosphoric acid,diluted or the spirit of vinegar of molar concentration 0.0001-0.1; With products therefrom with dissolution with solvents after, in above-mentioned solution, add halogenated alkane, its addition in mole be silane coupler 2-10 doubly, under 0-200 ℃ of temperature conditions, carried out quaterisation in back flow reaction 1-48 hour, the product of described quaterisation filmed on matrix after with dissolution with solvents obtain diaphragm, then 0-90 ℃, relative humidity be in the environment of 50-90% with the diaphragm drying, promptly obtain can be used for the adsorbent of Adsorption of Heavy Metal Ions; Described silane coupler is siloxanes or the halosilanes that contains the ammonia alkyl; Described acid anhydrides is phthalic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride or the pyrovinic acid acid anhydride that contains epoxy-terminated or side group.
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| CN102512976A (en) * | 2011-12-15 | 2012-06-27 | 合肥学院 | Preparation method of negative charge hybridization membrane material for removing heavy metal ions in water |
| CN102974315B (en) * | 2012-12-10 | 2014-08-20 | 中国矿业大学 | Load type amino functional meso-porous silicon adsorbent and preparation method thereof |
| CN103566907B (en) * | 2013-11-13 | 2015-07-08 | 济南大学 | Preparation method and application of pyromellitic dianhydride modified loofah sponge adsorbent |
| CN106311158B (en) * | 2016-09-07 | 2018-03-23 | 济南大学 | A kind of preparation method of maleic acid modified magnetic loofah adsorbent |
| CN106395965B (en) * | 2016-10-10 | 2019-06-18 | 天津工业大学 | A method of rich in thioamido functional magnetic material efficient absorption heavy metal |
| CN107417913B (en) * | 2017-08-22 | 2020-04-14 | 广东工业大学 | Nano organic microporous polymer and method for adsorbing heavy metals in drinking water |
| CN107376665A (en) * | 2017-09-13 | 2017-11-24 | 合肥学院 | Preparation method of chitosan-based organic-inorganic hybrid porous film |
| CN107583620B (en) * | 2017-10-23 | 2020-04-14 | 黄淮学院 | Chitosan-based metal ion adsorbent and preparation method thereof |
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| CN110605101A (en) * | 2019-10-08 | 2019-12-24 | 西安交通大学 | Adsorbent for adsorbing lead ions, and membrane protective agent and water treatment agent containing same |
| CN110732307B (en) * | 2019-10-28 | 2022-06-24 | 苏州科技大学 | Preparation method and application of EDTA (ethylene diamine tetraacetic acid) modified magnetic nanocomposite |
| CN114832790B (en) * | 2022-04-12 | 2023-08-15 | 南昌大学 | PEI@PMDA composite material and preparation method and application thereof |
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